Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
  • C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
  • C08G59/72—Complexes of boron halides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
  • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
  • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
  • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
  • H01L21/76841—Barrier, adhesion or liner layers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
  • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
  • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
  • H01L21/82—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices to produce devices, e.g. integrated circuits, each consisting of a plurality of components
  • H01L21/822—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices to produce devices, e.g. integrated circuits, each consisting of a plurality of components the substrate being a semiconductor, using silicon technology
  • H01L21/8221—Three dimensional integrated circuits stacked in different levels

Definitions

• the present invention includes MEMS (micro electro mechanical system) parts, micro machine parts, micro fluid parts, ⁇ -TAS (micro total analysis system) parts, ink jet printer parts, micro reactor parts, conductive layers, LIGA parts, micro injection molding. And high-resolution negative photosensitive resin compositions useful in the manufacture of molds and stamps for heat embossing, screens or stencils for micro printing applications, MEMS package parts, semiconductor package parts, BioMEMS and biophotonic devices, and printed wiring boards And a cured product of the negative photosensitive resin composition having high corrosion resistance under wet heat conditions and excellent adhesion to various substrates.
• MEMS micro electro mechanical system
• ⁇ -TAS micro total analysis system
• Photoresistable resists have recently been widely used in semiconductor and MEMS / micromachine applications. In such applications, photolithography processing is achieved by patterning exposure on a substrate and then developing with a developer to selectively remove exposed or non-exposed areas. Resist (photoresist) that can be processed by photolithography includes a positive type and a negative type. The exposed part dissolves in the developing solution is the positive type, and the one that becomes insoluble is the negative type.
• the aspect ratio is an important characteristic calculated by resist film thickness / pattern line width and showing the performance of photolithography.
• Photoresist polymerization initiators such as polyfunctional bisphenol A novolak type epoxy resin (trade name: EPON SU-8 resin, Resolution Performance Products), Dow Chemical's CYRACURE UVI-6974, etc.
• a negative-type chemically amplified photoresist composition comprising (this photocationic polymerization initiator is composed of a propylene carbonate solution of aromatic sulfonium hexafluoroantimonate).
• the photoresist composition is known as a photoresist composition that can be processed by thick film photolithography because it has very low light absorption in the wavelength range of 350 to 450 nm.
• a solid photoresist layer having a thickness of 100 ⁇ m or more can be formed by applying this photoresist composition on various substrates by a technique such as spin coating or curtain coating and then evaporating the solvent by baking.
• photolithography can be performed by irradiating near ultraviolet light through a photomask by various exposure methods such as contact exposure, proximity exposure, or projection exposure.
• a negative image of a high-resolution photomask can be formed on the substrate by immersing in a developing solution and dissolving the non-exposed areas.
• substrates such as MEMS parts, MEMS packages, and semiconductor packages are not limited to conventional silicon wafers, but various types of substrates such as silicon nitride and lithium tantalate. Etc. may be used. It is also required for the photoresist that the cured product has excellent adhesion to these substrates.
• Patent Document 1 discloses a photosensitive resin composition containing a photocationic polymerization initiator having a specific structure and a polyfunctional epoxy resin. In the examples, it is described that the cured product of the photosensitive resin composition is excellent in adhesion to a silicon wafer, but no mention is made of adhesion to a substrate other than the silicon wafer.
• the present invention has been made in view of the above circumstances, and is a negative photosensitive resin composition excellent in resolution and cured in excellent adhesion to various substrates other than silicon wafers and silicon wafers.
• the purpose is to provide.
• a negative photosensitive resin composition containing (A) an epoxy resin, (B) a compound having a phenolic hydroxyl group, and (C) a cationic photopolymerization initiator, 30% by mass or more of the (A) epoxy resin is Following formula (1) (In the formula (1), each R independently represents a glycidyl group or a hydrogen atom, and at least two of a plurality of R are glycidyl groups. A represents an average value of the number of repeating units; An epoxy resin (A-1) represented by the following formula: The compound (B) having a phenolic hydroxyl group is Following formula (2) (In formula (2), b is an average value and represents a real number in the range of 1 to 10.
• Each R 1 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• Compound (B-1) having a phenolic hydroxyl group Following formula (3) (In formula (3), c is an average value and represents a real number in the range of 1 to 10.
• R 2 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
• R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
• R 5 represents each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
• Compound (B-5) having phenolic hydroxyl group, and the following formula (7) In formula (7), h is an average value and represents a real number in the range of 1 to 10).
• Epoxy resin (A-2) represented by Following formula (10)
• m and n are average values and are real numbers in the range of 1 to 30, and R 9 and R 10 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or tri
• An epoxy resin (A-3) represented by Following formula (11) (In formula (11), p represents an average value and is a real number in the range of 1 to 30).
• the negative photosensitive resin composition of the present invention is excellent in resolution, excellent in adhesion to not only silicon wafers but also various substrates other than silicon wafers, and does not contain a highly toxic antimony compound. Since the load is small and corrosion of the metal can be suppressed, it is suitably used for MEMS parts, micromachine parts, semiconductor package parts, and the like.
• the negative photosensitive resin composition of the present invention comprises (A) an epoxy resin (hereinafter also simply referred to as “(A) component”), (B) a compound having a phenolic hydroxyl group (hereinafter simply referred to as “(B) component”. And (C) a photocationic polymerization initiator (hereinafter also simply referred to as “component (C)”).
• component (C) a photocationic polymerization initiator
• the (A) epoxy resin contained in the negative photosensitive resin composition of the present invention is an epoxy resin (A-1) in which 30% by mass or more of the (A) epoxy resin is represented by the formula (1). It is characterized by that.
• each R independently represents a glycidyl group or a hydrogen atom, and at least two of the plurality of Rs are glycidyl groups.
• a represents an average value of the number of repeating units, and is a real number in the range of 0 to 30.
• epoxy resin (A-1) represented by the formula (1) examples include KM-N-LCL (trade name, bisphenol A novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 195 to 210 g / eq., softening point 78 to 86 ° C.), Epicoat 157 (trade name, bisphenol A novolak type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 180 to 250 g / eq., softening point 80 to 90 ° C.), EPON SU- 8 (trade name, bisphenol A novolak type epoxy resin, manufactured by Resolution Performance Products, epoxy equivalent of 195 to 230 g / eq., Softening point of 80 to 90 ° C.), and the like.
• KM-N-LCL trade name, bisphenol A novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 195 to 210 g / eq., softening point 78 to 86 ° C.
• the epoxy resin represented by the formula (1) means an epoxy resin mainly composed of the epoxy resin represented by the formula (1) (although not particularly limited, 1)
• the ratio of the epoxy resin represented by 1) is preferably 80% by mass or more), including subcomponents produced when the epoxy resin is produced, and high molecular weight polymers of the epoxy resin. It is.
• the epoxy equivalent of the component (A) contained in the negative photosensitive resin composition of the present invention is preferably 150 to 500, and more preferably 150 to 450.
• the “epoxy equivalent of the component (A)” here means the epoxy equivalent of the mixture of all the epoxy resins contained in the negative photosensitive resin composition of the present invention.
• the molecular weight of the component (A) contained in the negative photosensitive resin composition of the present invention is preferably 500 to 15000, and more preferably 500 to 9000.
• “molecular weight of component (A)” means the average molecular weight of a mixture of all the epoxy resins contained in the negative photosensitive resin composition of the present invention.
• the softening point of the component (A) contained in the negative photosensitive resin composition of the present invention is preferably 40 to 120 ° C, and more preferably 55 to 110 ° C.
• the “softening point of component (A)” here means the softening point of a mixture of all the epoxy resins contained in the negative photosensitive resin composition of the present invention.
• the epoxy equivalent in this invention is the value measured by the method based on JISK7236
• molecular weight is the value of the weight average molecular weight computed in polystyrene conversion based on the measurement result of gel permeation chromatography.
• the softening point is a value measured by a method based on JIS K7234.
• the (A) epoxy resin contained in the negative photosensitive resin composition of the present invention only needs to be 30% by mass or more of the epoxy resin (A-1) represented by the formula (1). In other words, it may contain less than 70% by mass of an epoxy resin other than the epoxy resin (A-1) represented by the formula (1).
• the epoxy resin other than the epoxy resin (A-1) that can be contained in the epoxy resin is not particularly limited.
• long-chain bisphenol-type epoxy resins such as long-chain bisphenol A-type epoxy resins and long-chain bisphenol F-type epoxy resins
• novolaks obtained by reacting phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with formaldehyde in the presence of an acidic catalyst, and halohydrins such as epichlorohydrin and methylepichlorohydrin.
• novolak type epoxy resins obtained by reaction.
• the epoxy resins (A-2), (A-3), (A-4), (A), (C) have high chemical resistance, plasma resistance and transparency, and the cured product has low moisture absorption.
• One or more epoxy resins selected from the group consisting of A-5), (A-6), (A-7), (A-8) and (A-9) are preferred.
• One or more epoxy resins selected from the group consisting of (A-2) and (A-3) are more preferable, and (A-2) and (A-3) are mixed and used in (A-1). More preferably.
• R 6 , R 7 and R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• i represents an average value and is a real number in the range of 1 to 30.
• Specific examples of the epoxy resin (A-2) represented by the formula (9) include NC-3000 series such as NC-3000H (trade name, biphenyl-phenol novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy Equivalent 270 to 300 g / eq., Softening point 55 to 75 ° C.).
• m and n represent average values and are real numbers in the range of 1 to 30, and R 9 and R 10 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or trifluoro Indicates a methyl group.
• epoxy resin (A-3) represented by the formula (10) include NER-7604 and NER-7403 (both are trade names, bisphenol F type epoxy resins in which a part of the alcoholic hydroxyl group is epoxidized) Manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 200 to 500 g / eq., Softening point 55 to 75 ° C., NER-1302 and NER-7516 (both trade names, bisphenols in which a part of the alcoholic hydroxyl group is epoxidized) A-type epoxy resin, Nippon Kayaku Co., Ltd., epoxy equivalent 200 to 500 g / eq., Softening point 55 to 75 ° C.) and the like.
• p represents an average value and is a real number in the range of 1 to 30.
• Specific examples of the epoxy resin (A-4) represented by the formula (11) include EOCN-1020 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 190 to 210 g / eq., Softening point 55 to 85 ° C. ).
• the epoxy resin (A-5) is a reaction product of a phenol derivative represented by the above formula (12) and epihalohydrin.
• a phenol derivative represented by the formula (12) and an epihalohydrin such as epichlorohydrin and epibromohydrin
• a solvent capable of dissolving them After adding alkalis such as sodium hydroxide to the mixed solution and raising the temperature to the reaction temperature to perform addition reaction and ring closure reaction, the reaction solution is repeatedly washed with water, separated and the aqueous layer removed, and finally from the oil layer. The method of distilling a solvent off is mentioned.
• an epoxy resin (A-5) having different main components in the epoxy resin (A-5) can be obtained depending on the use ratio of the phenol derivative represented by the formula (12) and epihalohydrin used in the synthesis reaction. It has been. For example, when an excess amount of epihalohydrin is used with respect to the phenolic hydroxyl group of the phenol derivative, an epoxy resin mainly composed of a trifunctional epoxy resin in which all three phenolic hydroxyl groups in formula (12) are epoxidized (A-5) is obtained.
• the polyfunctional epoxy resin having a large molecular weight in which the phenolic hydroxyl groups of a plurality of phenol derivatives are bonded via epihalohydrin and the remaining phenolic hydroxyl groups are epoxidized. The content of increases.
• the epoxy resin (A-5) As a method of obtaining such an epoxy resin (A-5) mainly composed of a multimeric epoxy resin, in addition to the method of controlling by the use ratio of the phenol derivative and epihalohydrin, the epoxy resin (A-5) Further, a method in which a phenol derivative is further reacted can be mentioned.
• the epoxy resin (A-5) obtained by this method is also included in the category of the epoxy resin (A-5) contained in the photosensitive resin of the present invention.
• the reaction between the phenol derivative represented by the formula (12) and epihalohydrin is usually 0.3 to 30 mol, preferably 1 to 20 mol, more preferably 1 to 20 mol of epihalohydrin with respect to 1 mol of phenol derivative (corresponding to 3 mol of hydroxyl group). Is carried out using 3 to 15 moles.
• the epoxy resin (A-5) contained in the resin composition of the present invention is an epoxy resin obtained by the reaction of a phenol derivative represented by the formula (12) and an epihalohydrin, as long as it is a monomer of a phenol derivative.
• An epoxy resin (A-5) containing either an epoxy resin or a phenol derivative multimeric epoxy resin as a main component can be used.
• the epoxy resin (A-5) is excellent in solvent solubility and has a low softening point and is easy to handle, an epoxy resin of a phenol derivative monomer, an epoxy resin of a phenol derivative dimer (formula (12))
• An epoxy resin (A-5) containing as a main component any one of the above-mentioned epoxy resins is preferable.
• An epoxy resin (A-5) having a phenol derivative monomer epoxy resin or a phenol derivative dimer epoxy resin as a main component is more preferable.
• epoxy resin (A-5) which is a reaction product of the phenol derivative represented by the formula (12) and epihalohydrin
• NC-6300 trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 230 to 235 g / eq., Softening point 70 to 72 ° C.
• the epoxy resin (A-6) is a reaction product of an epoxy compound having at least two epoxy groups in one molecule and a compound having at least one hydroxyl group and one carboxyl group in one molecule; It is a reaction product with polybasic acid anhydride.
• Examples of the epoxy resin (A-6) include polycarboxylic acid epoxy compounds whose production methods are described in Japanese Patent No. 2698499.
• the epoxy equivalent and softening point can be variously adjusted depending on the epoxy resin used as a raw material of the epoxy resin (A-6) and the introduction rate of the substituent to be introduced.
• q represents an average value and is a real number in the range of 1 to 10.
• EPPN-201-L (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 180 to 200 g / eq., Softening point 65 to 78 ° C.).
• r represents an average value and is a real number in the range of 0.1 to 5.
• Specific examples of the epoxy resin (A-8) represented by the formula (14) include EPPN-501H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalents 162 to 172 g / eq., Softening point 51 to 57 ° C.
• EPPN-501HY (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 163 to 175 g / eq., Softening point: 57-63 ° C.), EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 158) To 178 g / eq., Softening point 60 to 72 ° C.).
• s represents an average value and is a real number in the range of 0.1 to 6.
• epoxy resin (A-9) represented by the formula (15) include XD-1000 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 245 to 260 g / eq., Softening point of 68 to 78 ° C. ).
• the compound (B) having a phenolic hydroxyl group contained in the negative photosensitive resin composition of the present invention is a compound (B-1) to (B-1) having a phenolic hydroxyl group represented by the above formulas (2) to (7). It contains one or more phenolic compounds selected from the group consisting of B-6).
• the hydroxyl equivalent of the component (B) is at least a predetermined preferable lower limit, good durability can be imparted to the cured product.
• the hydroxyl equivalent is not more than a predetermined preferable upper limit, the contribution to improving the strength of the cured film is maintained.
• the preferred hydroxyl equivalent of component (B) is 90 to 300, more preferably 90 to 250.
• the hydroxyl equivalent means a value measured by a method according to JIS K-0070.
• b is an average value and represents a real number in the range of 1 to 10.
• R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• Specific examples of the compound (B-1) having a phenolic hydroxyl group represented by the formula (2) include PN-152 (trade name, manufactured by Meiwa Kasei Co., Ltd., softening point 50 ° C., hydroxyl group equivalent 105 g / eq.), H-1 (trade name, manufactured by Meiwa Kasei Co., Ltd., softening point 80 ° C., hydroxyl group equivalent 103 g / eq.), TD-2131 (trade name, manufactured by DIC, softening point 80 ° C., hydroxyl group equivalent 105 g / eq.), KA -1160 (trade name, manufactured by DIC, softening point: 81 ° C., hydroxyl group equivalent: 117 g / eq.) And the like
• c is an average value and represents a real number in the range of 1 to 10.
• R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• Specific examples of the compound (B-2) having a phenolic hydroxyl group represented by the formula (3) include GPH-65 (trade name, manufactured by Nippon Kayaku Co., Ltd., softening point: 65 ° C., hydroxyl group equivalent: 200 g / eq. ), MEHC-7800H (trade name, manufactured by Meiwa Kasei Co., Ltd., softening point: 85 ° C., hydroxyl group equivalent: 179 g / eq.).
• d is an average value and represents a real number in the range of 1 to 10.
• R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• Specific examples of the compound (B-3) having a phenolic hydroxyl group represented by the formula (4) include MEHC-7851H (trade name, manufactured by Meiwa Kasei Co., Ltd., softening point 84 ° C., hydroxyl group equivalent 217 g / eq.), Etc. Is mentioned.
• e and f are average values and represent real numbers in the range of 1 to 10.
• R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• Specific examples of the compound (B-4) having a phenolic hydroxyl group represented by the formula (5) include MEHC-7841-4S (trade name, manufactured by Meiwa Kasei Co., Ltd., softening point: 65 ° C., hydroxyl group equivalent: 166 g / eq. ) And the like.
• g is an average value and represents a real number in the range of 1 to 10.
• R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• Specific examples of the compound (B-5) having a phenolic hydroxyl group represented by the formula (6) include KTG-105 (trade name, manufactured by Nippon Kayaku Co., Ltd., softening point: 103 ° C., hydroxyl equivalent: 105 g / eq. ), MEH-7500 (trade name, manufactured by Meiwa Kasei Co., Ltd., softening point: 109 ° C., hydroxyl group equivalent: 98 g / eq.), And the like.
• h is an average value and represents a real number in the range of 1 to 10.
• Specific examples of the compound (B-6) having a phenolic hydroxyl group represented by the formula (7) include MEH-7600-4H (trade name, manufactured by Meiwa Kasei Co., Ltd., softening point 154 ° C., hydroxyl group equivalent 101 g / eq. ) And the like.
• the component (B) contained in the negative photosensitive resin composition of the present invention includes compounds (B-1) to (B-6) having a phenolic hydroxyl group represented by the formulas (2) to (7). Other compounds having a phenolic hydroxyl group may be used in combination, and the compound that can be used in combination is not particularly limited.
• the component (B) does not need to be added in a large amount, and its blending ratio in the negative photosensitive resin composition of the present invention is 1 with respect to the sum of the components (A), (B) and (C). Thru
• or 35 mass% is preferable, More preferably, it is 5 to 25 mass%.
• the (C) cationic photopolymerization initiator contained in the negative photosensitive resin composition of the present invention contains the compound represented by the formula (8).
• (C) Photocationic polymerization initiator is a compound that generates cations upon irradiation with radiation such as ultraviolet rays, far ultraviolet rays, excimer lasers such as KrF and ArF, X-rays and electron beams, and the cations can serve as polymerization initiators. It is.
• Such a cationic photopolymerization initiator is usually also referred to as an energy sensitive acid generator.
• Specific examples of commercially available compounds represented by formula (8) include Irgacure PAG290 (trade name, BASF).
• the component (C) contained in the negative photosensitive resin composition of the present invention may be used in combination with a photocationic polymerization initiator other than the compound represented by the formula (8).
• the polymerization initiator is not particularly limited.
• the content of the component (C) in the negative photosensitive resin composition of the present invention is usually 0.2 to 5% by mass, preferably 0.5%, based on the total mass of the component (A) and the component (B). Thru
• a reactive epoxy monomer having miscibility may be added to improve pattern performance.
• the reactive epoxy monomer means a compound having a weight-average molecular weight of about 500 or less and having an epoxy group that is liquid or semi-solid at room temperature and deviates from the definition of the epoxy resin (A).
• a glycidyl ether compound which is liquid at room temperature can be used.
• glycidyl ether compound examples include diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, dimethylolpropane diglycidyl ether, polypropylene glycol diglycidyl ether (manufactured by ADEKA, ED506), trimethylolpropane triglycidyl ether (manufactured by ADEKA Corporation).
• the reactive epoxy monomer component is used for the purpose of improving the reactivity of the resist and the physical properties of the cured film.
• Many reactive epoxy monomer components are liquid.
• the blending ratio of the component is not particularly limited, but when the component is in a liquid state, it is not sticky to the film after removing the solvent by blending at 20% by mass or less with respect to the total amount of the negative photosensitive resin composition. It is desirable to avoid inconveniences such as occurrence of mask sticking and mask sticking. From this point, when the reactive epoxy monomer component is blended in the negative photosensitive resin composition, the blending ratio is preferably 10% by mass or less based on the total mass of the component (A) and the component (B). In particular, 7 mass% or less is suitable.
• a solvent may be added in order to lower the viscosity of the composition and improve the coating properties.
• organic solvents that are usually used in inks, paints, and the like, and can dissolve each constituent of the photosensitive resin composition can be used without any particular limitation.
• Specific examples of the solvent include ketones such as acetone, ethyl methyl ketone, cyclohexanone and cyclopentanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, ethylene glycol dimethyl ether, dipropylene glycol dimethyl ether and dipropylene glycol.
• Glycol ethers such as diethyl ether, ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, esters such as propylene glycol monomethyl ether acetate and ⁇ -butyrolactone, alcohols such as methanol, ethanol, cellosolve and methyl cellosolve, octane and Examples include aliphatic hydrocarbons such as decane, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. .
• solvents can be used alone or in admixture of two or more.
• the solvent component is added for the purpose of adjusting the film thickness and coating property when applied to the substrate.
• the amount used to properly maintain the solubility of the main component, the volatility of the component, the liquid viscosity of the composition, etc. is preferably 95% by mass or less, more preferably 10% in the negative photosensitive resin composition. Thru
• a miscible adhesion imparting agent may be used for the purpose of improving the adhesion of the composition to the substrate.
• a coupling agent such as a silane coupling agent or a titanium coupling agent can be used.
• a silane coupling agent is used.
• silane coupling agents include 3-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3 -Aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane and the like.
• adhesiveness imparting agents can be used alone or in combination of two or more. Since the adhesion-imparting agent is unreactive with the main component, components other than those that act at the substrate interface will be present as residual components after curing. Since the adhesion-imparting agent exhibits an effect even in a small amount depending on the base material, it is appropriate to use it within a range that does not affect the physical properties.
• the use ratio thereof is preferably 15% by mass or less, more preferably 5% by mass or less in the negative photosensitive resin composition.
• a sensitizer may be used for further absorbing ultraviolet light and supplying the absorbed light energy to the photocationic polymerization initiator.
• the sensitizer for example, thioxanthones and anthracene compounds having an alkoxy group at the 9th and 10th positions (9,10-dialkoxyanthracene derivatives) are preferable.
• alkoxy group C1-C4 alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, are mentioned, for example.
• the 9,10-dialkoxyanthracene derivative may further have a substituent.
• substituents examples include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group, an alkyl sulfonate group, and an alkyl carboxylate.
• An ester group etc. are mentioned.
• alkyl in the sulfonic acid alkyl ester group and the carboxylic acid alkyl ester group include alkyl having 1 to 4 carbon atoms such as methyl, ethyl, and propyl.
• the substitution position of these substituents is preferably the 2-position.
• thioxanthones include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and 2-isopropylthioxanthone.
• 2,4-diethylthioxanthone for example, trade name Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.
• 2-isopropylthioxanthone is preferable.
• Examples of the 9,10-dialkoxyanthracene derivative include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dimethoxy-2.
• sensitizer component can be used alone or in admixture of two or more. Most preferred is the use of 2,4-diethylthioxanthone and 9,10-dimethoxy-2-ethylanthracene. Since the sensitizer component exhibits an effect in a small amount, its use ratio is preferably 30% by mass or less, more preferably 20% by mass or less, relative to the component (C).
• trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, isopropoxydiethoxy are used when it is necessary to reduce the adverse effects caused by the ions derived from the component (C).
• Alkoxyaluminum such as aluminum and trisbutoxyaluminum
• Phenoxyaluminum such as trisphenoxyaluminum and trisparamethylphenoxyaluminum
• Trisacetoxyaluminum Trisstearatoaluminum, Trisbutyrataluminum, Trispropionatoaluminum
• Trisacetylacetonatoaluminum Tris Trifluoroacetylacetonatoaluminum, trisethylacetoacetatoaluminum, diacetylacetonatodipivaloyl Ion catcher, such as shelf preparative aluminum and diisopropoxy (ethylacetoacetato) an organoaluminum compound such as aluminum may be added.
• An ion catcher component can be used individually or in combination of 2 or more types. The compounding quantity may be 10 mass% or less with respect to the total solid (all components except a solvent) of the negative photosensitive resin composition of this invention
• thermoplastic resin examples include polyethersulfone, polystyrene, and polycarbonate.
• colorant examples include phthalocyanine blue, phthalocyanine green, iodin green, crystal violet, titanium oxide, carbon black, naphthalene black and the like.
• thickener examples include olben, benton, montmorillonite and the like.
• antifoaming agent examples include silicone-based, fluorine-based and polymer-based antifoaming agents.
• Examples of the negative photosensitive resin composition of the present invention include barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. Fillers can be added. The addition amount of the inorganic filler may be 60% by mass or less in the negative photosensitive resin composition of the present invention.
• the negative photosensitive resin composition of the present invention is composed of the essential components (A), (B) and (C), and, if necessary, a solvent, various additives and the like. It can be adjusted simply by mixing and stirring. You may disperse
• the negative photosensitive resin composition of the present invention is preferably used in the form of a solution to which a solvent is added.
• a solvent for example, a metal substrate such as silicon, aluminum, copper, gold, or platinum, a ceramic such as lithium tantalate, glass, silicon oxide, or silicon nitride.
• the negative photosensitive resin composition of the present invention can be applied to a thickness of 0.1 to 1000 ⁇ m on a substrate such as a substrate, polyimide, or polyethylene terephthalate using a spin coater. Subsequently, after removing the solvent under a heating condition of 60 to 130 ° C.
• a mask having a predetermined pattern is placed and irradiated with ultraviolet rays. be able to.
• the unexposed portion is developed using a developer at room temperature (for example, 15 ° C. or higher) to 50 ° C. for about 1 to 180 minutes. It can be developed to form a pattern.
• a heat treatment satisfying various characteristics can be obtained by heat treatment at 130 to 200 ° C.
• an organic solvent such as ⁇ -butyrolactone, triethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, or a mixed solution of the organic solvent and water can be used.
• a paddle type, spray type, shower type, or other developing device may be used, and ultrasonic irradiation may be performed as necessary.
• aluminum is mentioned as a preferable metal substrate in using the negative photosensitive resin composition of this invention.
• the negative photosensitive resin composition of the present invention is applied to the base film using a roll coater, die coater, knife coater, bar coater, gravure coater, etc., and then dried at 45 to 100 ° C.
• a dry film resist can be obtained by drying in an oven and removing a predetermined amount of solvent, or by laminating a cover film or the like as necessary. At this time, the thickness of the resist on the base film is adjusted to 2 to 100 ⁇ m.
• films, such as polyester, a polypropylene, polyethylene, TAC, a polyimide, are used, for example.
• the cover film is peeled off, transferred to a substrate at a temperature of 40 to 100 ° C. under a pressure of 0.05 to 2 MPa by a hand roll or a laminator, etc., and the negative photosensitive resist dissolved in the solvent.
• the exposure, post-exposure bake, development, and heat treatment may be performed as in the case of the conductive resin composition.
• the negative photosensitive resin composition is supplied as a dry film as described above, the steps of coating on the support and drying can be omitted. This makes it possible to more easily form a cured product pattern using the negative photosensitive resin composition of the present invention.
• MEMS package or a semiconductor package When used as a MEMS package or a semiconductor package, it can be used by coating with a negative photosensitive resin composition of the present invention or by producing a hollow structure.
• substrates for MEMS and semiconductor packages metal thin films of aluminum, gold, copper, chromium, titanium, etc. are formed on silicon wafers of various shapes by sputtering or vapor deposition to a thickness of 10 to 5000 mm, etching methods, etc. Thus, a substrate or the like obtained by finely processing the metal is used.
• silicon oxide or silicon nitride may be formed as an inorganic protective film with a thickness of 10 to 10,000 mm.
• a coating or hollow structure on the substrate in order to make or install a MEMS or semiconductor device and to shield the device from the outside air.
• the negative photosensitive resin composition of this invention can carry out by the above-mentioned method.
• a partition wall is formed on the substrate by the above-described method, and further, a dry film is laminated thereon and patterned so as to become a lid on the partition wall by the above-described method.
• a hollow package structure can be produced.
• a MEMS package part and a semiconductor package part satisfying various characteristics can be obtained by performing a heat treatment at 130 to 200 ° C. for 10 to 120 minutes as necessary.
• the “package” is a sealing method used to block the ingress of gas and liquid from the outside air in order to maintain the stability of the substrate, wiring, and elements.
• the package described in the present invention is performed in order to prevent deterioration of a package having a driving unit such as a MEMS, a hollow package for packaging a vibrator such as a SAW device, a semiconductor substrate, a printed wiring board, wiring, or the like. It represents surface protection, resin sealing, and the like.
• the “wafer level package” represents a package method in which a protective film, a terminal, wiring processing, and a package are performed in a wafer state and then cut into a chip.
• the negative photosensitive resin composition of the present invention and its cured product have excellent image resolution and corrosion resistance under wet heat conditions, and excellent adhesion to various substrates other than silicon wafers.
• the effect is expressed.
• the cured product of the photosensitive resin composition includes, for example, MEMS (micro electro mechanical system) parts, micro machine parts, micro fluid parts, ⁇ -TAS (micro total analysis system) parts, ink jet printer parts, micro reactor parts. , Conductive layers, LIGA parts, molds and stamps for micro injection molding and hot embossing, screens or stencils for micro printing applications, MEMS package parts, semiconductor package parts, BioMEMS and biophotonic devices, and production of printed wiring boards, etc. Used for The cured product of the photosensitive resin composition is particularly useful in MEMS package parts and semiconductor package parts.
• Examples 1 to 6 and Comparative Examples 1 to 3 (Preparation of a negative photosensitive resin composition) According to the blending amount shown in Table 1 (unit is part by mass), (A) an epoxy resin, (B) a compound having a phenolic hydroxyl group, (C) a photocationic polymerization initiator and other components were mixed in a flask equipped with a stirrer. The mixture was stirred and mixed at 2 ° C. for 2 hours to obtain a negative photosensitive resin composition for comparison with the present invention.
• the exposed substrate was post-exposure baked (PEB) at 95 ° C. for 6 minutes using a hot plate, and then developed at 23 ° C. for 6 minutes by an immersion method using propylene glycol monomethyl ether acetate.
• PEB post-exposure baked
• the adhesion force is the shear strength at the time when the pattern is peeled from the substrate by applying force from the side surface of the pattern using a shear tool.
• a higher value is preferable because the adhesion between the substrate and the resin composition is higher.
• a block resist pattern of 100 ⁇ m ⁇ 100 ⁇ m (film thickness is 20 ⁇ m) is formed on the substrate with the optimal exposure obtained above, and a bonding tester (manufactured by Resuka Co., Ltd.) is used.
• (A-1) to (F) are as follows.
• (A-1): Trade name KM-N-LCL, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 210 g / eq. , Softening point 85 ° C., compound represented by formula (1) (average number of repetitions a 4)
• (A-2): Trade name NC-3000H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 285 g / eq. , Softening point 65 ° C., compound represented by formula (9) (average number of repetitions i 2)
• C-1 Compound represented by formula (8), trade name: PAG-290 manufactured by BASF
• C-2 sulfonium salt photocationic polymerization initiator
• SP-172 manufactured by ADEKA
• the blending amount described in the table represents the solid content value.
• D Trade name EX-321L, manufactured by Nagase ChemteX Corporation, epoxy equivalent 140 g / eq.
• the negative photosensitive resin composition of the present invention (Examples 1 to 6) has higher adhesion to SiN than the negative photosensitive resin composition of Comparative Example 1, and Comparative Example 2 and It was revealed that the corrosion resistance to the Al substrate was higher than that of the negative photosensitive resin composition of No. 3.
• the negative photosensitive resin composition of the present invention (Example 1) was found to have higher adhesion to various types of substrates than the negative photosensitive resin composition of Comparative Example 1. It has been revealed.
• the negative photosensitive resin composition according to the present invention can form a pattern with high adhesion to various substrates, and is suitable for the field of MEMS package parts, semiconductor packages, and the like.
• the photosensitive resin composition of the present invention has both adhesion to various materials and low corrosiveness, which is advantageous for forming a cavity during molding.
• the cured product of the photosensitive resin composition includes, for example, a MEMS (micro electro mechanical system) part, a micro machine part, a micro fluid part, a ⁇ -TAS (micro total analysis system) part, an ink jet printer part, a micro reaction, and the like.

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• 2019
  • 2019-02-01 TW TW108104197A patent/TW201936688A/zh unknown
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